Surface Extraction Process During Initial Oxidation of Pt(111): Effect of Hydrophilic/Hydrophobic Cations in Alkaline Media.

The surface oxidation states of the metal electrodes affect the activity, selectivity, and stability of the electrocatalysts. Oxide formation and reduction on such electrodes must be comprehensively understood to achieve next-generation electrocatalysts with outstanding performance and stability. Herein, the initial electrochemical oxidation of Pt(111) in alkaline media containing hydrophilic and hydrophobic cations is investigated by X-ray crystal truncation rod (CTR) scattering, infrared (IR) spectroscopy, and nanoparticle-based surface-enhanced Raman spectroscopy (SERS). Structural determination using X-ray CTR revealed surface buckling and Pt extraction at the initial stage of surface oxidation, depending on the cationic species. Vibrational spectroscopy is performed to identify the potential- and cation-dependent formation of three oxide species (IR-active OHad, Raman-active OHad/Oad(H2O), and Raman-active Oad). Hydrophilic alkali metal cations (Li+) inhibit surface roughening via irreversible oxide formation. Hydrophilic Li+ can strongly stabilize IR-active OHad, hindering the extraction of Pt surface atoms. Interestingly, bulky hydrophobic cations such as tetramethylammonium (TMA+) cation also reduce the extent of irreversible oxidation despite the absence of IR-active OHad. Hydrophobic TMA+ inhibits the formation of Raman-active OHad/Oad(H2O) associated with Pt extraction. In contrast, the moderate hydrophilicity of K+ has no protective effect against irreversible oxidation. Moderate hydrophilicity enables the coadsorption of Raman-active OHad/Oad(H2O) and Raman-active Oad. The electrostatic repulsion between Raman-active OHad/Oad(H2O) and neighboring Raman-active Oad promotes Pt extraction. These results provide insights into controlling the surface structures of electrocatalysts using cationic species during the oxide formation and reduction processes.

Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111).

The proton-coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long-standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR-PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well-defined Pt(111). We unveil a dual-cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt-O and Pt-OH overlayers and ii) the competition between inner- and outer-sphere PCET steps. The cation-dependent transition from Pt-O to Pt-OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.

Fast-Decoding Algorithm for Electrode Processes at Electrified Interfaces by Mean-Field Kinetic Model and Bayesian Data Assimilation: An Active-Data-Mining Approach for the Efficient Search and Discovery of Electrocatalysts.

The microscopic origins of the activity and selectivity of electrocatalysts has been a long-lasting enigma since the 19th century. By applying an active-data-mining approach, employing a mean-field kinetic model and a statistical approach of Bayesian data assimilation, we demonstrate here a fast decoding to extract key properties in the kinetics of complicated electrode processes from current-potential profiles in experimental and literary data. As the proof-of-concept, kinetic parameters on the four-electron oxygen reduction reaction in the 0.1 M HClO4 solution (ORR: O2 + 4e- + 4H+ → 2H2O) of various platinum-based single-crystal electrocatalysts are extracted from our own experiments and third-party literature to investigate the microscopic electrode processes. Furthermore, data assimilation of the mean-field ORR model and experimental data is performed based on Bayesian inference for the inductive estimation of kinetic parameters, which sheds light on the dynamic behavior of kinetic parameters with respect to overpotential. This work shows that a fast-decoding algorithm based on a mean-field kinetic model and Bayesian data assimilation is a promising data-driven approach to extract key microscopic features of complicated electrode processes and therefore will be an important method toward building up advanced human-machine collaborations for the efficient search and discovery of high-performance electrochemical materials.

Tailoring the active site for the oxygen evolution reaction on a Pt electrode.

Highly active electrocatalysts for the oxygen evolution reaction (OER) are essential to improve the efficiency of water electrolysis. The properties of OER active sites on single-crystal Pt electrodes were examined herein. The OER is markedly enhanced by repeated oxidative and reductive potential cycles on the Pt(111) surface. The OER activity on Pt(111) is nine times higher in the third cycle than that before the potential cycles. OER activation by potential cycling depends on the (111) terrace width, with wider (111) terraces significantly enhancing the OER. The oxidation/reduction of the Pt(111) surface produces atomic-sized vacancies on the terraces that activate the OER. Structural analysis using X-ray diffraction reveals that the active sites formed by potential cycling are defects in the second subsurface Pt layer. Potential cycling induces the bowl-shaped roughening of the electrode surface, wherein high-coordination number Pt atoms at the bottom of the cavities activate the OER.

Effect of Hydrophobic Cations on the Inhibitors for the Oxygen Reduction Reaction on Anions and Ionomers Adsorbed on Single-Crystal Pt Electrodes.

Weakening of the poisoning by the specifically adsorbed anions assists in developing next-generation electrocatalysts for use in low-temperature fuel cells. In this study, we evaluated how hydrophobic cations with different alkyl chain lengths affect the oxygen reduction reaction (ORR) activities on the single-crystal Pt surfaces in contact with sulfuric acid solution and Nafion ionomers. Interfacial tetraalkylammonium cations with longer alkyl chains activated the ORR on the Pt(111) surface. In a solution containing tetrahexylammonium cations (THA+), the ORR activities on Pt(111) in sulfuric acid solution and on Nafion-modified Pt(111) in perchloric acid solution were four and eight times higher than those in the solutions without THA+, respectively. Infrared spectroscopy revealed the reduction of the amount of (bi)sulfate anions and the sulfonate group of Nafion adsorbed on Pt(111) due to the presence of THA+. The hydrophobic cations weaken the noncovalent interactions between specifically adsorbed species and promote the ORR.

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid-liquid interfaces.

Multi-electron, multi-proton transfer is important in a wide spectrum of processes spanning biological, chemical and physical systems. These reactions have attracted significant interest due to both fundamental curiosity and potential applications in energy technology. In this Perspective Review, we shed light on modern aspects of electrode processes in the 21st century, in particular on the recent advances and challenges in multistep electron/proton transfers at solid-liquid interfaces. Ongoing developments of analytical techniques and operando spectrometry at electrode/electrolyte interfaces and reliable computational approaches to simulate complicated interfacial electrochemical reactions enable us to obtain microscopic insights about these complex processes, such as the role of quantum effects in electrochemical reactions. Our motivation in this Perspective Review is to provide a comprehensive survey and discussion of state-of-the-art developments in experiments, materials, and theories for modern electrode process science, as well as to present an outlook for the future directions in this field.

Effect of hydrophobic cations on the oxygen reduction reaction on single‒crystal platinum electrodes.

Highly active catalysts for the oxygen reduction reaction are essential for the widespread and economically viable use of polymer electrolyte fuel cells. Here we report the oxygen reduction reaction activities of single‒crystal platinum electrodes in acidic solutions containing tetraalkylammonium cations with different alkyl chain lengths. The high hydrophobicity of a tetraalkylammonium cation with a longer alkyl chain enhances the oxygen reduction reaction activity. The activity on Pt(111) in the presence of tetra‒n‒hexylammonium cation is eight times as high as that without this cation, which is comparable to the activities on Pt3Co(111) and Pt3Ni(111) electrodes. Hydrophobic cations and their hydration shells destabilize the adsorbed hydroxide and adsorbed water. The hydrophobic characteristics of non‒specifically adsorbed cations can prevent the adsorption of poisoning species on the platinum electrode and form a highly efficient interface for the oxygen reduction reaction.

Interfacial Structure of PtNi Surface Alloy on Pt(111) Electrode for Oxygen Reduction Reaction.

The interfacial structure and activity for the oxygen reduction reaction (ORR) were investigated on a PtNi surface alloy on a Pt(111) electrode (PtNi/Pt(111)). The PtNi surface alloy was prepared by thermal annealing of Ni2+ modified on Pt(111) at 573-803 K. After optimizing the alloying temperature and the amount of added Ni, the ORR current density of PtNi/Pt(111) at 0.9 V (reversible hydrogen electrode) is enhanced 9.5 times compared with that of Pt(111), and the activity is decreased by 24% after 1000 potential cycles. The atomic composition and subsurface structure of PtNi/Pt(111) were determined by in situ infrared reflection-absorption spectroscopy and X-ray diffraction. The surface contains a (111)-oriented Pt-skin and the subsurface of the 2nd-5th layers of the PtNi alloy contains less than 11% Ni atoms. The layer spacings of the surface alloy layers are slightly expanded compared with those of bare Pt(111). Homogeneous alloying with a small amount of Ni in the subsurface layers achieves the high ORR activity and durability.